US12466909B2

US12466909B2 - Modified dicyclopentadiene-based resin

Info

Publication number: US12466909B2
Application number: US18/178,547
Authority: US
Inventors: Te-Chao Liao; Hung-Yi Chang; Yu-Ting Liu
Original assignee: Nan Ya Plastics Corp
Current assignee: Nan Ya Plastics Corp
Priority date: 2022-11-03
Filing date: 2023-03-06
Publication date: 2025-11-11
Also published as: CN117986505A; JP2024068074A; TWI828405B; US20240166788A1; TW202419499A

Abstract

A modified dicyclopentadiene-based resin is provided. The modified dicyclopentadiene-based resin is formed from a dicyclopentadiene-based resin having an amino group, a phenol and a polyoxymethylene by a cyclization reaction. The dicyclopentadiene-based resin having an amino group is formed by nitration reaction and hydrogenation reaction of dicyclopentadiene phenolic resin.

Description

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority benefit of Taiwan application serial no. 111141997, filed on Nov. 3, 2022. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.

BACKGROUND Technical Field

The invention relates to a dicyclopentadiene (DCPD-based resin, particularly to a modified dicyclopentadiene-based resin for which the structure includes a benzoxazine group.

Description of Related Art

Dicyclopentadiene-based resins have good insulation, corrosion resistance, dielectric constant (Dk) and dissipation factor (Df) and other characteristics, so it is usually applied in shipbuilding, automotive industry, optics, electronic products and other fields that require high temperature coatings. However, the dielectric properties of the currently used dicyclopentadiene-based resins limit their application to insulating materials for electronic substrates such as high frequency printed circuit boards.

SUMMARY

The invention provides a modified dicyclopentadiene-based resin capable of providing good dielectric properties and heat resistance.

A modified dicyclopentadiene-based resin of the invention is formed from a dicyclopentadiene-based resin having an amino group, a phenol and a polyoxymethylene (POM) by a cyclization reaction. The dicyclopentadiene-based resin having an amino group is formed by nitration reaction and hydrogenation reaction of dicyclopentadiene phenolic resin.

In an embodiment of the invention, a weight average molecular weight of the dicyclopentadiene phenolic resin is 400 to 2,000.

In an embodiment of the invention, a structure of the modified dicyclopentadiene-based resin has at least two benzoxazine groups.

In an embodiment of the invention, a ratio of a mole number of the dicyclopentadiene phenolic resin, a mole number of the phenol to a mole number of the polyoxymethylene is 1:1:2 to 1:2:4.

In an embodiment of the invention, a weight average molecular weight of the modified dicyclopentadiene-based resin is 800 to 20,000.

A modified dicyclopentadiene-based resin of the invention has a structure represented by Formula (1) as follows:

- in Formula (1), L represents a dicyclopentadienylene group, a divalent organic group derived from a phenol-based compound or a combination thereof,
- L¹and L²each represent a divalent organic group derived from a phenol-based compound, and,
- m represents an integer from 0 to 10.

In an embodiment of the invention, a precursor of the modified dicyclopentadiene-based resin includes a dicyclopentadiene phenolic resin. A weight average molecular weight of the dicyclopentadiene phenolic resin is 400 to 2,000.

In an embodiment of the invention, the phenol-based compound includes phenol.

In an embodiment of the invention, the L represents

or a combination thereof, and * represents a bonding position.

In an embodiment of the invention, the L¹and L²each represent

and * represents a bonding position.

Based on the above, the invention provides a dicyclopentadiene-based resin for which the structure has a benzoxazine group, which has good dielectric properties and heat resistance.

To make the features and advantages of the disclosure to be comprehended more easily, embodiments are described in detail as follows.

DESCRIPTION OF THE EMBODIMENTS

The following are embodiments describing the content of the invention in detail. The implementation details provided in the embodiments are for illustrative purposes, and are not intended to limit the scope of protection of the content of the invention. Those with ordinary knowledge in the art may modify or change these implementation details according to the needs of the actual implementation.

The “divalent organic group” as used in the specification is an organic group having two bonding positions. And the “divalent organic group” may form two chemical bonds through these two bonding positions.

The invention provides a modified dicyclopentadiene-based resin formed from a dicyclopentadiene-based resin having an amino group, a phenol and a polyoxymethylene by a cyclization reaction, wherein the dicyclopentadiene-based resin having an amino group is formed by nitration reaction and hydrogenation reaction of dicyclopentadiene phenolic resin.

A structure of the modified dicyclopentadiene-based resin of the invention has a benzoxazine group, preferably has at least two benzoxazine groups, more preferably has at least three benzoxazine groups. For example, the benzoxazine group may bond on a terminal (e.g. terminal on both sides) and/or a branch of the modified dicyclopentadiene-based resin, preferably bond on terminal on both sides and the branch of the resin. More preferably, after the dicyclopentadiene phenolic resin finished the reaction, hydroxyl groups of all phenol groups in a structure thereof are substituted to benzoxazine groups. That is, a structure of the modified dicyclopentadiene-based resin does not have hydroxyl group. Thus, the modified dicyclopentadiene-based resin have good dielectric properties and heat resistance.

A weight average molecular weight of the dicyclopentadiene phenolic resin is 400 to 2,000, preferably 400 to 1,000. For example, specific examples of commercially available products of dicyclopentadiene resin having a phenol group may include ERM6105 (trade name; manufactured by SONGWON Co., Ltd.; weight average molecular weight: 800), ERM6115 (trade name; manufactured by SONGWON Co., Ltd.; weight average molecular weight: 1,100), ERM6140 (trade name; manufactured by SONGWON Co., Ltd.; weight average molecular weight: 1,300) or other suitable dicyclopentadiene phenolic resin.

First, the dicyclopentadiene-based resin having an amino group is formed by performing a dicyclopentadiene phenolic resin to nitration reaction and hydrogenation reaction. The method of nitration reaction and hydrogenation reaction of the dicyclopentadiene phenolic resin is not particularly limited, for example, well-known nitration reaction and hydrogenation reaction may be performed, which will not be described in detail here. In this embodiment, the hydrogenation reaction may be performed in a solvent of tetrahydrofuran, toluene, isopropanol, dimethylacetamide, or a combination thereof, preferably performed in a solvent of dimethylacetamide. For example, in a mixed solvent of toluene and isopropanol, a volume ratio of toluene to isopropanol may be 80:20 to 100:0. In a mixed solvent of dimethylacetamide and toluene, a volume ratio of dimethylacetamide to toluene may be 75:25 to 100:0. Thereby, the hydrogenation reaction may achieve a good hydrogenation rate, for example, which may be 90% or more, more preferably 98% or more). Next, the dicyclopentadiene-based resin having an amino group, a phenol and a polyoxymethylene are performed to a cyclization reaction to form a modified dicyclopentadiene-based resin. In this embodiment, the cyclization reaction may be performed in a solvent of toluene, ethanol, dimethylacetamide, or a combination thereof, preferably performed in a solvent of dimethylacetamide. For example, in a mixed solvent of toluene and ethanol, a volume ratio of toluene to ethanol may be 60:40 to 100:0. In this embodiment, a ratio of a mole number of the dicyclopentadiene phenolic resin, a mole number of the phenol to a mole number of the polyoxymethylene is 1:1:2 to 1:2:4, preferably 1:1:2 to 1:1.5:3.

The modified dicyclopentadiene-based resin has a structure represented by Formula (1) as follows. In this embodiment, a weight average molecular weight of the modified dicyclopentadiene-based resin is 800 to 20,000, preferably 800 to 5,000.

In Formula (1), L represents a dicyclopentadienylene group, a divalent organic group derived from a phenol-based compound or a combination thereof, preferably a combination of the dicyclopentadienylene group and the divalent organic group derived from the phenol-based compound, and the divalent group is preferably a divalent group including a benzoxazine group;

- L¹and L²each represent a divalent organic group derived from a phenol-based compound; and
- m represents an integer from 0 to 10, preferably an integer from 0 to 5.

In this embodiment, the phenol-based compound may include phenol. L, L′ and L 2 may represent a divalent group derived from phenol. In this embodiment, L may represent

or a combination thereof, preferably a combination of

represents a bonding position. L¹and L²may each represent

* represents a bonding position.

In this embodiment, the modified dicyclopentadiene-based resin has a structure represented by Formula (2) as follows. In this embodiment, the modified dicyclopentadiene-based resin may also be a modified benzoxazine (BX) resin, a modified multi-benzoxazine resin or a benzoxazine resin modified by dicyclopentadiene (abbreviated as DCPD-BX).

In formula (2), m represents an integer from 0 to 10, preferably an integer from 0 to 5.

Examples of Modified Dicyclopentadiene-Based Resin

Example 1 to Example 3 of the modified dicyclopentadiene-based resin are described below:

Example 1

Dicyclopentadiene phenolic resin including 1 mole hydroxyl group (trade name: ERM6105, manufactured by SONGWON Co., Ltd.; weight average molecular weight: 800) was added in 6 mole of dimethylacetamide (DMAC) to dissolve therein. Next, 1.25 mole of potassium carbonate and 1.25 mole of 4-fluoronitrobenzene were added thereto, and reacted at a temperature of 120° C. for 5 hours, and then cooled to room temperature. Then, filtration was performed to remove solids, followed by precipitation with a mixed solution of methanol and water to obtain a precipitate of nitrated dicyclopentadiene phenolic resin (DCPD-NO₂). Next, the precipitate was added to dimethylacetamide, and reacted at a temperature of 90° C. for 8 hours to perform a hydrogenation reaction and obtain a dicyclopentadiene-based resin having an amino group (DCPD-NH₂). Then, the dicyclopentadiene-based resin having an amino group, 1 mole of phenol and 2 mole of polyoxymethylene were added to dimethylacetamide, and reacted at a temperature of 80° C. for 8 hours. The modified dicyclopentadiene-based resin of Example 1 was obtained, whose structure has benzoxazine groups bonded to the terminal of both sides and branches of the structure (DCPD-BX) and may have a structure represented by Formula (2) (m representing an integer from 0 to 6). The obtained modified dicyclopentadiene-based resin was evaluated by each of the following evaluation methods, and the results thereof are as shown in Table 1.

Example 2

The modified dicyclopentadiene-based resin of Example 2 was prepared using the same steps as Example 1, and the difference thereof is: changing to use dicyclopentadiene phenolic resin (trade name: ERM6115, manufactured by SONGWON Co., Ltd.; weight average molecular weight: 1,100) as reactant. The obtained modified dicyclopentadiene-based resin (which may have a structure represented by Formula (2), and wherein m represents an integer from 0 to 8) was evaluated by each of the following evaluation methods, and the results thereof are as shown in Table 1.

Example 3

The modified dicyclopentadiene-based resin of Example 3 was prepared using the same steps as Example 1, and the difference thereof is: changing to use dicyclopentadiene phenolic resin (trade name: ERM6140, manufactured by SONGWON Co., Ltd.; weight average molecular weight: 1,300) as reactant. The obtained modified dicyclopentadiene-based resin (which may have a structure represented by Formula (2), and wherein m represents an integer from 0 to 10) was evaluated by each of the following evaluation methods, and the results thereof are as shown in Table 1.

TABLE 1

Example 1	Example 2	Example 3

Weight average molecular	800	1,100	1,300
weight of dicyclopentadiene
phenolic resin
Dielectric constant (Dk)	4.0	3.8	3.5
Dissipation factor (Df)	0.0048	0.0046	0.0040
Tg (unit: ° C.)	280	264	232
Peel strength (unit: lb/in)	5.8	5.5	5.0

<Evaluation Methods>
a. Dielectric Constant (Dk)

The prepared modified dicyclopentadiene-based resin was coated on a substrate, and baked at a temperature of 120° C. for 2 minutes, and then hot pressed at a temperature of 210° C. for 3 hours to form a film with thickness of 100 μm. Next, the film was measured for a dielectric constant (Dk) at a frequency of 10 GHz via a dielectric analyzer (model: E4991A; manufactured by Agilent Technologies, Inc.). When the dielectric constant is smaller, the modified dicyclopentadiene-based resin has good dielectric property.

b. Dissipation Factor (Df)

The prepared modified dicyclopentadiene-based resin was coated on a substrate, and baked at a temperature of 120° C. for 2 minutes, and then hot pressed at a temperature of 210° C. for 3 hours to form a film with thickness of 100 μm. Next, the film was measured for a dissipation factor (Df) at a frequency of 10 GHz via a dielectric analyzer (model: E4991A; manufactured by Agilent Technologies, Inc.). When the dissipation factor is smaller, the modified dicyclopentadiene-based resin has good dielectric property.

c. Glass Transition Temperature (Tg)

The prepared modified dicyclopentadiene-based resin was measured for a glass transition temperature (Tg) via a dynamic mechanical analyzer (DMA). When the Tg is greater, the modified dicyclopentadiene-based resin has good resistance to phase changes, that is, good heat resistance.

- Heating rate: 10° C./min
- Temperature range: 30° C. to 300° C. (heating, cooling, heating)
  d. Peel Strength

The prepared modified dicyclopentadiene-based resin was coated on a substrate, and baked at a temperature of 120° C. for 2 minutes to form a resin film. Then, copper foils were laminated on an upper surface and a lower surface of the resin film, and hot pressed at a temperature of 210° C. for 3 hours to form a film with thickness of 200 μm. Next, the film was measured for a peel strength via a universal tensile machine. When the peel strength is greater, the modified dicyclopentadiene-based resin has good resistance to peeling from the substrate, that is, good peel resistance.

It may be seen from Table 1 that when the modified dicyclopentadiene-based resin has a structure having a benzoxazine group, and a number of benzoxazine group is at least 3 (that is, the terminal of both sides and a branch of the resin have benzoxazine group) (Examples 1-3), the modified dicyclopentadiene-based resin has good heat resistance, peel resistance and dielectric properties at the same time.

In addition, compared to the modified dicyclopentadiene-based resin obtained by using the dicyclopentadiene phenolic resin with a larger weight average molecular weight as the precursor, the modified dicyclopentadiene-based resin obtained by using the dicyclopentadiene phenolic resin with a smaller weight average molecular weight as the precursor has greater glass transition temperature and greater peel strength, that is, better heat resistance and peel resistance, and good dielectric properties at the same time.

In addition, compared to the modified dicyclopentadiene-based resin obtained by using the dicyclopentadiene phenolic resin with a smaller weight average molecular weight as the precursor, the modified dicyclopentadiene-based resin obtained by using the dicyclopentadiene phenolic resin with a larger weight average molecular weight as the precursor has smaller dielectric constant and smaller dissipation factor, that is, better dielectric properties, and good heat resistance and peel resistance at the same time.

Based on the above, the modified dicyclopentadiene-based resin of the invention is formed from a dicyclopentadiene-based resin having an amino group, a phenol and a polyoxymethylene by a cyclization reaction, for which the structure has a benzoxazine group, so it has good heat resistance, peel resistance and dielectric properties. Therefore, the modified dicyclopentadiene-based resin has good applicability.

Although the invention has been disclosed in the embodiments above, they are not intended to limit the invention. Anyone with ordinary knowledge in the relevant technical field can make changes and modifications without departing from the spirit and scope of the invention. The scope of protection of the invention shall be subject to those defined by the claims attached.

Claims

What is claimed is:

1. A modified dicyclopentadiene-based resin, formed from a dicyclopentadiene-based resin having an amino group, a phenol and a polyoxymethylene by a cyclization reaction,

wherein the dicyclopentadiene-based resin having an amino group is formed by nitration reaction and hydrogenation reaction of dicyclopentadiene phenolic resin.

2. The modified dicyclopentadiene-based resin according to claim 1, wherein a weight average molecular weight of the dicyclopentadiene phenolic resin is 400 to 2,000.

3. The modified dicyclopentadiene-based resin according to claim 1, a structure thereof has at least two benzoxazine groups.

4. The modified dicyclopentadiene-based resin according to claim 1, wherein a ratio of a mole number of the dicyclopentadiene phenolic resin, a mole number of the phenol to a mole number of the polyoxymethylene is 1:1:2 to 1:2:4.

5. The modified dicyclopentadiene-based resin according to claim 1, a weight average molecular weight thereof is 800 to 20,000.

6. A modified dicyclopentadiene-based resin, having a structure represented by Formula (1) as follows:

in Formula (1), L represents a dicyclopentadienylene group, a divalent organic group derived from a phenol-based compound or a combination thereof,

L¹and L²each represent a divalent organic group derived from a phenol-based compound, and

m represents an integer from 0 to 10.

7. The modified dicyclopentadiene-based resin according to claim 6, a precursor thereof comprising a dicyclopentadiene phenolic resin, a weight average molecular weight of the dicyclopentadiene phenolic resin is 400 to 2,000.

8. The modified dicyclopentadiene-based resin according to claim 6, wherein the phenol-based compound comprises phenol.

9. The modified dicyclopentadiene-based resin according to claim 6, wherein L represents

or a combination thereof, and * represents a bonding position.

10. The modified dicyclopentadiene-based resin according to claim 6, wherein L¹and L²each represent

and * represents a bonding position.